Carbamoylimidazole derivatives

ABSTRACT

Novel carbamoylimidazole derivatives of the formula (I) ##STR1## in which R 1  represents lower alkyl, lower alkoxy-lower alkyl or cycloalkyl having 3 to 8 carbon atoms, 
     R 2  represents fluoro-substituted lower alkyl, 
     X represents oxygen or sulfur, 
     Y represents halogen or lower alkyl, 
     m represents the numbers 0, 1 or 2, and 
     n represents the numbers 2, 3, 4, 5 or 6, 
     and the use of the new compounds as agricultural and horticultural fungicides.

This is a division of application Ser. No. 774,206, filed Sept. 9, 1985, now U.S. Pat. No. 4,609,669.

The present invention relates to novel carbamoylimidazole derivatives, to processes for their preparations and to their use as agricultural and horticultural fungicides.

It has already been disclosed that certain carbamoylimidazole derivatives have fungicidal activities (see Japanese Laid-Open Patent Application 31047/1975, resp. Great Britain patent application No. 1 469 772).

There have been found novel carbamoylimidazole derivatives of the formula (I) ##STR2## in which R¹ represents lower alkyl, lower alkoxy-lower alkyl, or cycloalkyl having 3 to 8 carbon atoms,

R² represents fluoro-substituted lower alkyl,

X represents oxygen or sulfur.

Y represents halogen or lower alkyl.

m represents the numbers 0, 1 or 2, and

n represents the numbers 2, 3, 4, 5 or 6.

Carbamoylimidazole derivatives of the formula (I) are obtained when

(a) the compounds of the formula (II) ##STR3## wherein R¹, R², X, Y, m and n are as defined above, are reacted with N,N'-carbonyldiimidazole of the formula ##STR4## if appropriate in the presence of acid acceptors and inert solvents, or

(b) the compounds of the formula (IV) ##STR5## wherein R¹, R², X, Y, m and n are as defined above, are reacted with the imidazole compounds of the formula (V) ##STR6## wherein M represents a hydrogen atom or an alkali metal atom, if appropriate in the presence of acid acceptors and inert solvents.

The novel carbamoylimidazole derivatives of the general formula (I) exhibit powerful agricultural and horticultural fungicidal properties.

Surprisingly, the compounds according to the invention exhibit a substantially greater fungicidal action in the field of agriculture and horticulture than those known from the aforementioned prior art.

Though the generic scope of the compounds of the aforementioned prior art conceptually embraced the compounds of the formula (I) according to the invention, the specification of the prior art fails to give any specific description or suggestion on the present invention.

Among the carbamoylimidazole derivatives of the formula (I), preferred compounds are those in which

R¹ represents alkyl with 1 to 4 carbon atoms, alkoxy-alkyl with altogether 2 to 4 carbon atoms or cycloalkyl with 5 to 6 carbon atoms,

R² represents fluoroalkyl with 1 to 4 carbon atoms and 1 to 3 fluorine atoms,

Y represents chlorine or methyl, and

X, m and n have the meanings given above.

Particularly preferred are such compounds of the general formula (I), in which

R¹ represents alkyl with 1 to 4 carbon atoms, alkoxy-alkyl with altogether 2 to 4 carbon atoms or cyclopentyl,

R² represents trifluoro-substituted alkyl with 1 to 4 carbon atoms,

X represents oxygen or sulfur,

Y represents chlorine or methyl,

m represents the numbers 0, 1 or 2, and

n represents the numbers 2, 3 or 4.

Very particularly preferred carbamoylimidazole derivatives of the formula (I) are those in which

R¹ represents alkyl with 3 to 4 carbon atoms or ethoxy-ethyl,

R² represents trifluoromethyl or 2,2,2-trifluoroethyl,

X represents oxygen or sulfur,

Y represents chlorine,

m represents the numbers 0, 1 or 2 and

n represents the number 2.

Specifically, the following compounds may be mentioned:

1-<N-2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)phenoxy]-ethyl-N-propyl-carbamoyl>-imidazole,

1-<N-2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)phenoxy]-ethyl-N-sec-butyl-carbamoyl>-imidazole,

1-[N-2-(4-trifluoromethylthiophenoxy)-ethyl-N-sec-butyl-carbamoyl]-imidazole,

1-<N-2-[2,6-dichloro-4-(trifluoromethylthio)-phenoxy]-ethyl-N-propyl-carbamoyl>-imidazole,

1-[N-3-(4-trifluoromethylthiophenoxy)-propyl-N-sec-butyl-carbamoyl]-imidazole,

1-[N-5-(4-trifluoromethylthiophenoxy)-pentyl-N-propyl-carbamoyl]-imidazole,

1-[N-2-(4-trifluoromethoxyphenoxy)-ethyl-N-propylcarbamoyl]-imidazole,

1-[N-2-(2,6-dichloro-4-trifluoromethoxyphenoxy)-ethyl-N-propyl-carbamoyl]-imidazole and

1-[N-3-(4-trifluoromethoxyphenoxy)-propyl-N-sec-butyl-carbamoyl]-imidazole.

If, for example, N-<2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl>-N-propylamine and N,N'-carbonyldiimidazole are used as starting materials, the course of the reaction variant (a) can be represented by the following equation: ##STR7##

If, for example, N-(sec.-butyl)-N-[(4-trifluoromethoxy)-phenoxy-ethyl]-amidoformic acid chloride and imidazole are used as starting materials, the course of the reaction variant (b) can be represented by the following equation: ##STR8##

As starting materials in the reaction variant (a) according to the invention, the compounds of the general formula (II) are required. In this formula R¹, R², X, Y, m and n preferably have the meanings already given above in connection with the preferred meanings of the substituents in the general formula (I).

The compounds of the general formula (II) are novel and are obtained by reacting compounds of the formula (VI) ##STR9## wherein R², X, Y, m and n are as defined above, and

Hal represents a halogen atom,

with amino compounds of the formula (VII)

    R.sup.1 --NH.sub.2                                         (VII)

wherein R¹ is as defined above.

The intermediates of the general formula (VI) are also novel. They are obtained when compounds of the formula (VIII) ##STR10## wherein R², X, Y and m are as defined above, are reacted with dihalogeno compounds of the formula (IX)

    Hal--(CH.sub.2).sub.n --Hal                                (IX)

wherein n and Hal are as defined above,

if appropriate, in presence of acid acceptors and inert solvents.

As examples of the novel intermediates of the formula (VI) the following compounds may be mentioned:

2-[4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl bromide,

2-[4-(2,2,2-trifluoroethylthio)-2-tolyloxy]-ethyl bromide,

2-[4-(2,2,2-trifluoroethylthio)-3,5-xylyloxy]-ethyl bromide,

2-[2-chloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl bromide,

2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl bromide

3-[4-(2,2,2-trifluoroethylthio)-phenoxy]-propyl bromide

3-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-propyl bromide,

4-[4-(2,2,2-trifluoroethylthio)-phenoxy]-butyl bromide,

4-[4-(2,2,2-trifluoroethylthio)-2-tolyloxy]-butyl bromide,

4-[4-(2,2,2-trifluoroethylthio)-3,5-xylyloxy]-butyl bromide,

4-[2-chloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-butyl bromide,

2-(4-trifluoromethylthiophenoxy)-ethyl bromide,

2-(2-chloro-4-trifluoromethylthiophenoxy)-ethyl bromide,

2-(2,6-dichloro-4-trifluoromethylthiophenoxy)-ethyl bromide,

3-(4-trifluoromethylthiophenoxy)-propyl bromide,

3-(2-chloro-4-trifluoromethylthiophenoxy)-propyl bromide,

3-(2,6-dichloro-4-trifluoromethylthiophenoxy)-propyl bromide,

4-(4-trifluoromethylthiophenoxy)-butyl bromide,

4-(2-chloro-4-trifluoromethylthiophenoxy)-butyl bromide,

2-(4-trifluoromethoxyphenoxy)-ethyl bromide

2-(2-chloro-4-trifluoromethoxyphenoxy)-ethyl bromide,

2-(2,6-dichloro-4-trifluoromethoxyphenoxy)-ethyl bromide,

3-(4-trifluoromethoxyphenoxy)-propyl bromide,

3-(2-chloro-4-trifluoromethoxyphenoxy)-propyl bromide, and

3-(2,6-dichloro-4-trifluoromethoxyphenoxy)-propyl bromide.

The compounds of the formula (VIII) are partically already known (see Japanese Laid-Open Patent Applications 222094/1983 and 151151/1977. As example, there may be mentioned:

4-(2,2,2-trifluoroethylthio)-phenol,

4-(2,2,2-trifluoroethylthio)-2-methyl-phenol

4-(2,2,2-trifluoroethylthio)-3,5-dimethyl-phenol,

2-chloro-4-(2,2,2-trifluoroethylthio)-phenol,

2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenol,

4-trifluoromethylthio-phenol,

2-chloro-4-trifluoromethylthio-phenol,

2,6-dichloro-4-trifluoromethylthio-phenol,

4-trifluoromethoxy-phenol,

2-chloro-4-trifluoromethoxy-phenol and

2,6-dichloro-4-trifluoromethoxy-phenol.

Some of these compounds are novel. As an example, 2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenol is novel and may be prepared by using the well-known 2,6-dichlorophenol (see Beilstein, main volume (Hauptwerk) H6, page 190) as starting material, which is reacted with chlorosulfonic acid and the 2,6-dichloro-4-chlorosulfonyl-phenol obtained is reduced with zinc and sulfuric acid, and the 2,6-dichloro-4-mercapto-phenol obtained is reacted thereafter with 2,2,2-trifluoroethyl benzenesulfonate in the presence of potassium carbonate in dimethylformamide, resulting in the novel compound of the formula ##STR11##

The processes mentioned above are already known in general (see, for example, J. Org. Chem. 31, 2672-74 (1966) and Organic Syntheses, Coll. Vol. 1, pages 504-506).

2,6-Dichloro-4-trifluoromethylthio-phenol is also novel and may be produced by using trifluoroiodomethane in place of 2,2,2-trifluoroethyl-benzenesulfonate in accordance with the above-mentioned reaction.

2,6-Dichloro-4-trifluoromethoxy-phenol is also novel and the course of the reactions for its preparation can be explained as follows: 4-(Trifluoromethoxy)-phenol which is already known (see J. Org. Chem. 44, 2907-10 (1979)) is chlorinated in carbon tetrachloride yielding 2-chloro-4-(trifluoromethoxy)-phenol (at about 20° to 30° C.) and 2,6-dichloro-4-(trifluoromethoxy)-phenol (at the boiling point of the reaction mixture).

The dihalogeno-compounds of the general formula (IX) are well-known, as examples there may be mentioned:

Ethylene bromide,

propylene bromide, and

butylene bromide.

The formula (VII) provides a general definition of the amino compounds required as primary products in the reaction variant (a). In this formula R¹ preferably has the meanings already given above. As examples of the well known compounds of the formula (VII) may be mentioned:

methylamine,

ethylamine,

n-propylamine,

iso-propylamine,

n-butylamine,

sec.-butylamine,

2-ethoxyethylamine,

cyclopentylamine, and

cyclohexylamine.

The compounds of the general formula (II) explained above in connection with the reaction variant (a) are also starting materials needed to prepare the compounds of the general formula (IV). The last-mentioned compounds which are the starting materials in the reaction variant (b) are obtained by reaction of the novel compounds of the general formula (II) with phosgene or with diphosgene (i.e. trichloromethyl chloroformate), preferably in a solvent such as benzene or toluene at temperatures between 40° and 120° C. (see also the preparation examples).

The imidazolyl compounds of the formula (V) are also needed as starting materials in the reaction variant (b) according to the instant invention.

In this formula M preferably means hydrogen (this means imidazole itself is preferred), sodium and potassium.

The process for the production of the compounds of the general formula (I) according to process variant (a) may be carried out desirably in a solvent or diluent. Suitable diluents are all inert solvents. These include water; aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethylene and chlorobenzene; ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and ethyl isobutyl ketone; nitriles such as acetonitrile, propionitrile and acrylonitrile; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; esters such as ethyl acetate and amyl acetate; acid amides such as dimethylformamide and dimethylacetamide; sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane; and bases such as pyridine.

The process according to variant (a) may be carried out in the presence of an acid acceptor. Examples of acid acceptors include the hydroxides, carbonates, bicarbonates and alcoholates of alkali metals and tertiary amines such as triethylamine, diethylaniline and pyridine, all of which are generally known.

The process according to variant (a) can be carried out over a wide temperature range. Generally, it can be carried out at a temperature between about -20° C. and the boiling point of the mixture, desirably between about 0° C. and about 100° C. Desirably, the reaction is carried out under normal atmospheric pressure, but it is also possible to operate under elevated or reduced pressures.

In carrying out reaction variant (a) according to the invention, said reaction may be carried out without separating the compounds of the formula (II) as an intermediate. Alternatively, said intermediates of the formula (II) may also be separated.

Reaction variant (b) according to the invention is preferably carried out in the presence of a solvent or diluent. Preferred solvents or diluents in the process are any of inert solvents as described hereinbefore for reaction variant (a). Likewise, reaction variant (b) is preferably carried out in the presence of acid acceptors as described above for reaction variant (a).

Reaction variant (b) can be carried out over a wide temperature range, for example at a temperature between -20° C. and the boiling point of the mixture, preferably between 0° and 100° C. The reaction variant (b) is carried out under normal (ambient) pressure, but it is also possible to operate under elevated or reduced pressures.

The reaction for the preparation of the novel intermediates of the general formula (VI), i.e. the reaction of the compounds of the formula (VIII) with the dihalogeno compounds of the formula (IX), are also preferably carried out in the presence of a solvent or diluent. Preferred solvents or diluents in the process are any of inert solvents as described hereinbefore for reaction variant (a). Likewise, the reaction is preferably carried out in the presence of an acid acceptor as described hereinbefore for reaction variant (a). The temperatures can be held within a wide range, for example at a temperature between -20° C. and the boiling point of the mixture, preferably between 0° and 100° C. The reaction is carried out under normal (ambient) pressure, but it is also possible to operate under elevated or reduced pressures.

The carbamoylimidazole derivatives according to the invention exhibit powerful fungicidal effects in the field of agriculture and horticulture. They can therefore be used as agricultural and horticultural fungicides.

Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bacterial agents are employed in plant protection for combating Pseudomonadaceae, Phizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some causative organisms of fungal and bacterial diseases which fall under generic names listed above may be mentioned as examples, but not by way of limitation: Botrytis species, such as, for example, Botrytis cinerea; Plasmopara species, such as, for example, Plasmopara viticola; Uromyces species, such as, for example, Uromyces appendiculatus; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Venturia species, such as, for example, Venturia inaequalis; Podosphaera species, such as, for example, Podosphaera leucotricha; Phytophthora species, such as, for example, Phytophthora infestans; Erysiphe species, such as, for example, Erysiphe graminis; Puccinia species, such as, for example, Puccinia recondita; Fusarium species, such as, for example, Fusarium culmorum; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Septoria species, such as, for example, Septoria nodorum; Tilletia species, such as, for example, Tilletia caries; Xanthomonas species, such as, for example, Xanthomonas oryzae; Pseudomonas species, such as, for example: Pseudomonas lachrymans; Pyricularia species, such as, for example, Pyricularia oryzae, Pellicularia species, such as, for example, Pellicularia sasakii; Pyrenophora species, such as, for example, Pyrenophora teres (conidia form Drechslera, Syn. Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form Drechslera, Syn. Helminthosporium); Cercospora species, such as, for example, Cercospora canescens.

In particular, the carbamoylimidazole derivatives according to the general formula (I) exhibit an outstanding efficacy against blast of rice (Pyricularia oryzae), brown spot of rice (Helminthosporium oryzae), "bakanae" disease of rice (Gibberella fujikuroi), stem rot (Sclerotinia sclerotiorum), leaf blight (Alternaria brassicae), powdery mildew (Sphaerotheca fuliquinea) and gray mold (Botrytis cinerea) of various crops, anthracnose (Colletotrichum lagenarium) of cucumber, melon and the like, and late blight (Phytophthora infestans) of tomato.

As an agricultural and horticultural fungicide, the compounds of the formula (I) in accordance with this invention may be used directly upon dilution with water, or in various formulations obtained by methods generally practiced in the production of agricultural chemicals using agriculturally acceptable adjuvants. In actual use, these various formulations may be applied directly or after diluting them with water to the desired concentrations.

The agricultrual acceptable adjuvants as referred to herein include, for example, diluents (solvents, extenders, carriers), surface-active agents (solubilizing agents, emulsifiers, dispersing agents, wetting agents), stabilizers, stickers, aerosol propellants and synergists.

Examples of the solvents are water; furthermore organic solvents, such as hydrocarbons, for example n-hexane, petroleum ether, petroleum fractions, for example paraffin waxes, kerosene, light oils, middle oils and heavy oils, benzene, toluene, and xylene, furthermore halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, ethylene chloride, ethylene dibromide, chlorobenzene and chloroform, alcohols such as methanol, ethanol, propanol and ethylene glycol, ethers such as diethyl ether, ethylene oxide and dioxane, alcohol ethers such as ethylene glycol monomethyl ether, ketones such as acetone and isophorone, esters such as ethyl acetate and amyl acetate, amides such as dimethylformamide and dimethylacetamide and sulfoxides such as dimethyl sulfoxide.

Examples of the extenders or carriers include inorganic powders, for example sulfur, slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite, diatomaceous earth, amorphous silica, alumina, zeolites, and clay minerals (such as pyrophyllite, talc, montmorillonite, beidellite, vermiculite, kaolinite and mica); vegetable powders such as cereal powders, starches, processed starches, sugar, glucose and crushed stalks of plants; and powders of synthetic resins such as phenolic resins, urea resins, and vinyl chloride resins.

Examples of the surface-active agents include anionic surface-active agents such as alkylsulfonic acid esters (such as sodium laurylsulfate), arylsulfonic acids (such as alkylarylsulfonic acid salts and sodium alkylnaphthalenesulfonates), succinic acid salts, and salts of sulfuric acid esters of polyethylene glycol alkylaryl ethers; cationic surface-active agents such as alkylamines (for example laurylamine, stearyl trimethyl ammonium chloride and alkyl dimethylbenzyl ammonium chloride) and polyoxyethylene alkylamines; nonionic surface-active agents such as polyoxyethylene glycol ethers (for example polyoxyethylene alkylaryl ethers and the condensation products thereof), polyoxyethylene glycol esters (for example polyoxyethylene fatty acid esters), and polyhydric alcohol esters for example polyoxyethylene sorbitan monolaurate); and amphoteric surface-active agents.

Examples of other adjuvants include stabilizers; stickers (such as agricultural soaps, casein lime, sodium alginate, polyvinyl alcohol, vinyl acetate-type adhesives and acrylic adhesives); aerosol propellants (such as trichlorofuoromethane, dichlorofluoromethane, 1,2,2-trichloro-1,1,2-trifluoroethane, chlorobenzene, and lower ethers); combustion controlling agents for fumigants (such as nitrites, zinc powder, and dicyandiamide); oxygen-yielding agents (such as chlorates); effectprolonging agents; dispersion stabilizers (such as casein, tragacanth, carboxymethyl cellulose and polyvinyl alcohol); and synergists.

The compounds of this invention can be formulated into various forms by methods generally practiced in the production of agricultural chemicals. Illustrative of such forms are emulsifiable concentrates, oil preparations, wettable powders, soluble powders, suspensions, dusts, granules, pulverulent preparations, fumigants, tablets, aerosols, pastes and capsules.

The agricultural and horticultural fungicide of this invention may contain about 0.1 to about 95% by weight, preferably about 0.5 to about 90% by weight, of the aforesaid active ingredient.

In actual use, the suitable amount of the active compound in the aforesaid various formulations and ready-to-use preparations is generally about 0.0001 to about 20% by weight, preferably about 0.005 to about 10% by weight.

The content of the active ingredient can be properly varied depending upon the type of the formulation, the method, purpose, time and locus of its application, the state of occurrence of diseases.

If required, the compounds of this invention may be used in combination with other agricultural chemicals, for example insecticides, other fungicides, miticides, nematocides, antiviral agents, herbicides, plant growth regulators and attractants, such as organophosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organochlorine compounds, dinitro compounds, organosulfur or organometallic compounds, antibiotics, substituted diphenyl ether compounds, urea compounds and triazine compounds, and/or fertilizers.

Various formulations and ready-to-use preparations containing the aforesaid active ingredient of the invention can be applied by various methods generally practiced in the field of agricultural chemical application, for example spraying (liquid spraying, misting, atomizing, dusting, granule scattering, water surface application, pouring, etc.); soil application (mixing, sprinkling, vaporing and pouring etc.); surface application (such as coating, banding, dust coating and covering); and dipping. It can also be used by the so-called ultralow volume spraying method. According to this method, the active ingredient may be used in an amount of almost 100%.

The reate of application per unit area can be properly chosen, and is, for example, about 0.03 to about 10 kg, preferably about 0.3 to about 6 kg, per hectare.

According to this invention, there can be provided an agricultural and horticultural fungicidal composition comprisin the compound of general formula (I) as an active ingredient and a diluent (a solvent and/or an extender and/or a carrier) and/or a surface-active agent, and if further required, a stabilizer, a sticker and a synergist.

This invention also provides a method for controlling a crop disease, which comprises applying to a pathogen and/or the locus of its occurrence and/or the locus of occurrence of a crop disease, the compound of general formula (I) either singly or in admixture with a diluent (a solvent and/or an extender and/or a carrier) and/or surface-active agent and if further required, a stabilizer, a sticker and a synergist.

The following examples illustrate the present invention specifically. It should be noted however that the invention is not limited to them alone.

PREPARATION EXAMPLES: EXAMPLE 1 ##STR12##

To 2.16 g of crude N-<2-[2,6-dichloro-4-(2,2,2,-trifluoroethylthio)-phenoxy]-ethyl>-N-(propyl)-amine were added 10 ml of toluene and 1.7 g of N,N'-carbonyldiimidazole. The mixture was stirred at 50° C. for 3 hours and then under reflux for 6 hours. After cooling, 60 ml of toluene were added. The mixture was washed with water and dried over anyhydrous sodium sulfate. Evaporation of toluene gave 2.2 g of 1-<N-2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]ethyl-N-propyl-carbamoyl>-imidazole with the refractive index of n_(D) ²⁰ =1.5491.

The following compounds of the general formula (I) ##STR13## were obtained by the method described in Example 1:

    ______________________________________                                         Com-                                                                           pound                                    Physical                              No.   R.sup.1     n     Y.sub.m XR.sup.2 constant                              ______________________________________                                         2     CH.sub.3    2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5462                                3     C.sub.2 H.sub.5                                                                            2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5395                                4     C.sub.3 H.sub.7iso                                                                         2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5314                                5     C.sub.3 H.sub.7n                                                                           2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5332                                6     C.sub.4 H.sub.9sec                                                                         2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5295                                7     C.sub.4 H.sub.9n                                                                           2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5256                                8     C.sub.2 H.sub. 4 OC.sub.2 H.sub.5                                                          2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5274                                       ##STR14##  2     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 · 1.5460       10    C.sub.3 H.sub.7n                                                                           2     2-CH.sub.3                                                                             SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5345                                11    C.sub.4 H.sub.9sec                                                                         2     2-CH.sub.3                                                                             SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5313                                12    C.sub.4 H.sub.9sec                                                                         2     3,5-(CH.sub.3).sub.2                                                                   SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5330                                13    C.sub.3 H.sub.7n                                                                           2     2-Cl    SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5462                                14    C.sub.4 H.sub.9sec                                                                         2     2-Cl    SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5420                                15    C.sub.4 H.sub.9sec                                                                         2     2,6-Cl.sub.2                                                                           SCH.sub.2 CF.sub. 3                                                                     n.sub.D.sup.2 ·                                                       15460                                 16                                                                                    ##STR15##  2     2,6-Cl.sub.2                                                                           SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 · 1.5592       17    C.sub.3 H.sub.7n                                                                           3     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5310                                18    C.sub.4 H.sub.9sec                                                                         3     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5260                                19                                                                                    ##STR16##  3     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 · 1.5415       20    C.sub.3 H.sub.7n                                                                           3     2,6-Cl.sub.2                                                                           SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5498                                21    C.sub.4 H.sub.9sec                                                                         3     2,6-Cl.sub.2                                                                           SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5430                                22                                                                                    ##STR17##  3     2,6-Cl.sub.2                                                                           SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5570                                23    C.sub.3 H.sub.7n                                                                           4     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5260                                24    C.sub.4 H.sub.9sec                                                                         4     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5252                                25                                                                                    ##STR18##  4     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 · 1.5390       26    C.sub.3 H.sub.7n                                                                           4     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5280                                27    C.sub.4 H.sub.9sec                                                                         4     2-CH.sub.3                                                                             SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5250                                28    C.sub.3 H.sub.7n                                                                           4     3,5-(CH.sub.3).sub.2                                                                   SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5300                                29    C.sub.4 H.sub.9sec                                                                         4     3,5-(CH.sub.3).sub.2                                                                   SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5266                                30    C.sub.3 H.sub. 7n                                                                          4     2-Cl    SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5380                                31    C.sub.4 H.sub.9sec                                                                         4     2-Cl    SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5358                                32    C.sub.3 H.sub.7n                                                                           5     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5260                                33    C.sub.4 H.sub.9sec                                                                         5     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5245                                34    C.sub.4 H.sub.9sec                                                                         5     2,6-Cl.sub.2                                                                           SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5395                                35    C.sub.3 H.sub.7n                                                                           6     --      SCH.sub.2 CF.sub.3                                                                      n.sub.D.sup.2 ·                                                       1.5245                                36    C.sub.3 H.sub.7n                                                                           2     --      SCF.sub.3                                                                               m.p.                                                                           81-                                                                            82° C.                         37    C.sub.4 H.sub.9sec                                                                         2     --      SCF.sub.3                                                                               n.sub.D.sup. 2 ·                                                      1.5247                                38                                                                                    ##STR19##  2     --      SCF.sub.3                                                                               m.p. 90- 91° C.                39                                                                                    ##STR20##  2     --      SCF.sub.3                                                                               n.sub.D.sup.2 · 1.5375       40    C.sub.3 H.sub.7n                                                                           2     2-Cl    SCF.sub.3                                                                               m.p.                                                                           98-                                                                            99° C.                         41    C.sub.4 H.sub.9sec                                                                         2     2-Cl    SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5240                                42    C.sub.3 H.sub.7n                                                                           2-    2,6-Cl.sub.2                                                                           SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5410                                43    C.sub.4 H.sub.9sec                                                                         2     2,6-Cl.sub.2                                                                           SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5188                                44                                                                                    ##STR21##  2     2,6-Cl.sub.2                                                                           SCF.sub.3                                                                               n.sub.D.sup.2 · 1.5483       45    C.sub.3 H.sub.7n                                                                           3     --      SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5220                                46    C.sub.4 H.sub.9sec                                                                         3     --      SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5142                                47                                                                                    ##STR22##  3     --      SCF.sub.3                                                                               m.p. 83- 84° C.                48    C.sub.3 H.sub.7n                                                                           3     2-Cl    SCF.sub.3                                                                               m.p.                                                                           101-                                                                           102° C.                        49    C.sub.4 H.sub.9sec                                                                         3     2-Cl    SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5284                                50    C.sub.3 H.sub.7n                                                                           3     2,6-Cl.sub.2                                                                           SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5390                                51    C.sub.4 H.sub.9sec                                                                         3     2,6-Cl.sub.2                                                                           SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5341                                52                                                                                    ##STR23##  3     2,-Cl.sub.2                                                                            SCF.sub.3                                                                               m.p. 92- 93° C.                53    C.sub.3 H.sub.7n                                                                           4     --      SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5225                                54    C.sub.4 H.sub.9sec                                                                         4     --      SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5170                                55                                                                                    ##STR24##  4     --      SCF.sub.3                                                                               n.sub.D.sup.2 · 1.5330       56    C.sub.3 H.sub.7n                                                                           4     2-Cl    SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5310                                57    C.sub.4 H.sub.9sec                                                                         4     2-Cl    SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5298                                58    C.sub.3 H.sub.7n                                                                           5     --      SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5209                                59    C.sub.4 H.sub.9sec                                                                         5     --      SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5186                                60                                                                                    ##STR25##  5     --      SCF.sub.3                                                                               n.sub.D.sup.2 · 1.5303       61    C.sub.3 H.sub.7n                                                                           5     2-Cl    SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5291                                62    C.sub.4 H.sub.9sec                                                                         5     2-Cl    SCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5273                                63    C.sub.4 H.sub.9sec                                                                         5     2,6-Cl.sub.2                                                                           SCF.sub.3                                                                               n.sub.D.sup.2                                                                  1.5323                                64    C.sub.3 H.sub.7n                                                                           2     --      OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5000                                65    C.sub.4 H.sub.9sec                                                                         2     --      OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.4963                                66    C.sub.3 H.sub.7n                                                                           2     2-Cl    OCF.sub.3                                                                               m.p.                                                                           77-                                                                            78° C.                         67    C.sub.4 H.sub.9sec                                                                         2     2-Cl    OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5044                                68    C.sub.3 H.sub.7n                                                                           2     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5163                                69    C.sub.4 H.sub.9sec                                                                         2     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub. D.sup.2 ·                                                      1.5122                                70                                                                                    ##STR26##  2     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 · 1.5275       71    C.sub.3 H.sub.7n                                                                           3     --      OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.4978                                72    C.sub.4 H.sub.9sec                                                                         3     --      OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.4947                                73    C.sub.3 H.sub.7n                                                                           3     2-Cl    OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5097                                74    C.sub.4 H.sub.9sec                                                                         3     2-Cl    OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5057                                75    C.sub.3 H.sub.7n                                                                           3     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5146                                76    C.sub.4 H.sub.9sec                                                                         3     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5112                                77                                                                                    ##STR27##  3     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                                m.p. 80- 82° C.               78    C.sub.3 H.sub.7n                                                                           5     --      OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.4955                                79    C.sub.4 H.sub.9sec                                                                         5     --      OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.4942                                80    C.sub.3 H.sub.7n                                                                           5     2-Cl    OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5050                                81    C.sub.4 H.sub.9sec                                                                         5     2-Cl    OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5036                                82    C.sub.3 H.sub.7n                                                                           5     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5096                                83    C.sub.4 H.sub.9sec                                                                         5     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 ·                                                       1.5075                                84                                                                                    ##STR28##  5     2,6-Cl.sub.2                                                                           OCF.sub.3                                                                               n.sub.D.sup.2 ·              ______________________________________                                                                                  1.5160                                 Note: The symbol "--" in the column of Y.sub.m means there is no               Ysubstituent and the meaning of m is 0 (zero).                           

PREPARATION OF THE STARTING PRODUCTS (preparation of compounds of the general formulae II, VI and VIII) EXAMPLE II-1 ##STR29##

5 g of n-Propylamine were added to 2.38 g of 2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl bromide, and the mixture was stirred at room temperature for 8 hours and then under reflux for 3 hours. The excess of n-propylamine was evaporated. To the residue were added 20 ml of water, 20 ml of a 5% aqueous solution of potassium hydroxide and 100 ml of toluene. The mixture was stirred, and the organic layer was separated, washed with water and dried over anhydrous sodium sulfate. Low-boiling compounds were evaporated under reduced pressure. There were obtained 2.16 g of crude N-{2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl}-N-(propyl)-amine having a refractive indes of n_(D) ²⁰ =1.5210, which were used without further purification) for the preparation of compound No. 1 shown above.

EXAMPLE VI-1 ##STR30##

To an ethanol solution of sodium ethylate obtained by dissolving 0.7 g of metallic sodium in 50 ml of ethanol were added 8.9 g of 2,6-dichloro-4-(2,2,2,-trifluoroethylthio)-phenol and 20 g of ethylene bromide. The mixture was stirred at 40° C. for 2 hours and under reflux for 4 hours. Ethanol and the excess of ethylene bromide were evaporated. The residue was taken into 150 ml of toluene, washed with a 5% aqueous solution of potassium hydroxide and water in this sequence, and dried over anhydrous sodium sulfate. Toluene was evaporated, and the residue was distilled under reduced pressure to give 7.2 g of 2-[2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenoxy]-ethyl bromide with the b.p.=124°-126° C./0.8 mmHg.

The following compounds of the formula (VIa) (this means compounds of the general formula (VI) wherein "Hal" is Br) ##STR31## were obtained by the method described in Example VI-1:

    ______________________________________                                         Compound                                                                               n      Y.sub.m    X--R.sup.2                                                                               b.p. °C./mmHg                       ______________________________________                                         VI-2    2      --         --SCH.sub.2 CF.sub.3                                                                     136-139/10                                 VI-3    3      --         --SCH.sub.2 CF.sub.3                                                                     140-144/10                                 VI-4    4      --         --SCH.sub.2 CF.sub.3                                                                     143-145/5                                  VI-5    5      --         --SCH.sub.2 CF.sub.3                                                                     135-140/1.5                                VI-6    6      --         --SCH.sub.2 CF.sub.3                                                                     145-150/1.5                                VI-7    2      2-CH.sub.3 --SCH.sub.2 CF.sub.3                                                                     114-116/0.8                                VI-8    4      2-CH.sub.3 --SCH.sub.2 CF.sub.3                                                                     126-129/0.8                                VI-9    2      3,5-(CH.sub.3).sub.2                                                                      --SCH.sub.2 CF.sub.3                                                                     123-125/2                                  VI-10   4      3,5-(CH.sub.3).sub.2                                                                      --SCH.sub.2 CF.sub.3                                                                     132-134/1                                  VI-11   2      2-Cl       --SCH.sub.2 CF.sub.3                                                                     118-120/0.8                                VI-12   4      2-Cl       --SCH.sub.2 CF.sub.3                                                                     135-137/1                                  VI-13   2      2,6-Cl.sub.2                                                                              --SCH.sub.2 CF.sub.3                                                                     124-126/0.8                                VI-14   3      2,6-Cl.sub.2                                                                              --SCH.sub.2 CF.sub.3                                                                     151-153/1.5                                VI-15   4      2,6-Cl.sub.2                                                                              --SCH.sub.2 CF.sub.3                                                                     137-139/0.8                                VI-16   5      2,6-Cl.sub.2                                                                              --SCH.sub.2 CF.sub.3                                                                     143-145/0.6                                VI-17   2      --         --OCF.sub.3                                                                               90- 91/0.4                                VI-18   3      --         --OCF.sub.3                                                                              105-106/3.8                                VI-19   5      --         --OCF.sub.3                                                                              133-135/3.7                                VI-20   2      2-Cl       --OCF.sub.3                                                                              105-107/3.7                                VI-21   3      2-Cl       --OCF.sub.3                                                                              118-119/3.7                                VI-22   5      2-Cl       --OCF.sub.3                                                                              144-146/3.7                                VI-23   2      2,6-Cl.sub.2                                                                              --OCF.sub.3                                                                              111-113/3.7                                VI-24   3      2,6-Cl.sub.2                                                                              --OCF.sub.3                                                                              125-127/3.7                                VI-25   4      2,6-Cl.sub.2                                                                              --OCF.sub.3                                                                              136-138/3.7                                VI-26   5      2,6-Cl.sub.2                                                                              --OCF.sub.3                                                                              145-148/3.7                                VI-27   2      --         --SCF.sub.3                                                                               85-90/0.75                                VI-28   3      --         --SCF.sub.3                                                                              105-108/0.82                               VI-29   4      --         --SCF.sub.3                                                                              105-108/0.75                               VI-30   5      --         --SCF.sub.3                                                                              115-120/0.75                               VI-31   2      2-Cl       --SCF.sub.3                                                                              105-106/0.75                               VI-32   3      2-Cl       --SCF.sub.3                                                                              116-117/0.68                               VI-33   4      2-Cl       --SCF.sub.3                                                                              134-136/0.6                                VI-34   5      2-Cl       --SCF.sub.3                                                                              140-142/0.75                               VI-35   2      2,6-Cl.sub.2                                                                              --SCF.sub.3                                                                              114-116/0.75                               VI-36   3      2,6-Cl.sub.2                                                                              --SCF.sub.3                                                                              113-120/0.6                                VI-37   4      2,6-Cl.sub.2                                                                              --SCF.sub.3                                                                              130-132/0.75                               VI-38   5      2,6-Cl.sub.2                                                                              --SCF.sub.3                                                                              142-145/0.64                               ______________________________________                                          Note:                                                                          The symbol "--" in the column of Y.sub.m  means there is no Ysubstituent       and the meaning of m is 0(zero).                                         

EXAMPLE VIII-1 ##STR32##

Gaseous chlorine was slowly introduced to a stirred solution of 35.6 g of 4-trifluoromethoxyphenol in 100 ml carbon tetrachloride. The reaction temperature was kept at 20° to 30° C. by outer cooling. After saturaring with chlorine, the reaction mixture was stirred at 20° to 30° C. for 1 hour, cooled, washed with water, dried over anhydrous sodium sulfate, and evaporated to give a pale yellow residue. The residue was distilled under reduced pressure to give 29.8 g of 2-chloro-4-trifluoromethoxyphenol which boiled at 67°-70° C./18 mmHg.

EXAMPLE VIII-2 ##STR33##

To a boiling solution of 21.3 g of 2-chloro-4trifluoro-methoxyphenol, 2 g of anhydrous ferric chloride and 100 ml of carbon tetrachloride were introduced more than 8 g of gaseous chlorine over 1 hour. The reaction mixture was boiled another 1 hour, cooled, washed with water, dried over anhydrous sodium sulfate, and evaporated to give a pale yellow residue. The residue was distilled under reduced pressure (18 mmHg) and 9 g of a fraction which boiled at 96° to 99° C. was collected. When cooled, the fraction solidified. It melted at 42°-44° C.

EXAMPLE VIII-3 ##STR34##

64 g of potassium carbonate were added to a solution of 41.9 g of 3,5-dichloro-4hydroxy-benzenethiol in 200 ml of N,N-dimethylformamide under nitrogen atmosphere. To the stirred mixture were dropped at 30° to 40° C. 55 g of 2,2,2-trifluoroethyl-benzenesulfonate. The whole was stirred at 60° to 70° C. for 6 hours, cooled, mixed with 1.5 l of water, and acidified to pH 2 by dropwise addition of hydrochloric acid. A resulted oil was extracted with toluene and the toluene extract was washed with water. The washed toluene extracted was stirred with 160 ml of a 25% aqueous potassium hydroxide solution, and a water layer was separated. Then the separated water layer was acidified to pH 2 by adding hydrochloric acid. A resulted oil was extracted with toluene. The toluene extract was washed with water, dried over anhydrous sodium sulphate, and evaporated to give a residue. The residue was distilled under reduced pressure to give 42.3 g of 2,6 -dichloro-4-(2,2,2-trifluoroethylthio)-phenol which boiled at 85° to 88° C./1 mmHg.

EXAMPLE VIII-4 ##STR35##

In the same way as shown in Example VIII-3, by using trifluoroiodomethane in place of 2,2,2-trifluoroethyl-benzenesulfonate, 2,6-dichloro-4-trifluoromethylthio-phenol with the b.p. 110°-112° C./18 mm Hg and the m.p. 38°-40° C. was prepared.

USE EXAMPLES

The known comparison compounds are identified as follows: ##STR36##

Both compounds shown above are described in the Japanese Laid Open Application 31047/1975 resp. the GB-PS 1 469 779.

EXAMPLE A Rice blast (Pyricularia oryzae) test (testing by spraying on stalks and leaves)

Active compound: 50 parts by weight

Carrier: 45 parts by weight of a 1:5 mixture of of diatomaceous earth and kaolin

Emulsifier: 5 parts by weight of polyoxyethylene alkyl phenyl ether

The active compound, carrier and emulsifier in the the amounts indicated above were pulverized and mixed to form a wettable powder. The test chemical was prepared by diluting a predetermined amount of the wettable powder with water.

Testing method:

Aquatic rice plants (variety: Asahi) were cultivated in unglazed pots having a diameter of 12 cm, and 3- to 4-leaf stage, a dilution to a predetermined concentration of the test chemical prepared as above was sprayed at a rate of 50 ml per three pots. On the next day, a suspension of artificially cultivated spores of Pyricularia oryzae was inoculated (twice) by spraying. The pots were maintained in a humid chamber kept at a relatively humidity of 100% and a temperature of 25° C. to infect the plants with the fungus. Seven days after the inoculation, the degree of the disease per pot was evaluated and rated on the following standard, and the control index (%) was calculated. The phytotoxicity was also examined.

    ______________________________________                                                        Percentage of the area                                          Degree of disease                                                                             of leasions (%)                                                 ______________________________________                                         0              0                                                                 0.5          2 or less                                                       1              3-5                                                             2               6-10                                                           3              11-20                                                           4              21-40                                                           5              41 or more                                                      ______________________________________                                          ##STR37##                                                                

In the present test, three pots constituted one treatment The results are shown in the following Table:

                  TABLE A                                                          ______________________________________                                         Rice blast (Pyricularia oryzae) test                                                         Concentration of the                                                                         Control                                                          active ingredient                                                                            index                                              Compound No.  ppm           (%)                                                ______________________________________                                         A-1           250            40                                                (Comparison                                                                    compound)                                                                       1            250           100                                                16            250           100                                                18            250           100                                                21            250           100                                                23            250           100                                                31            250           100                                                40            250           100                                                42            250           100                                                46            250           100                                                65            250           100                                                68            250           100                                                ______________________________________                                    

EXAMPLE B Late blight of tomato (Phytophtora infestans) test

Each of the test compounds in the form of an emulsion prepared in accordance with Example (b) (see hereinafter) was sprayed by a spray gun on tomato (variety: Kurihara) grown in 9 cm unglazed pots. One day after the spraying, a suspension of spores of the present pathogen was inoculated and the pots were left to stand overnight in a constant temperature chamber kept at a temperature of 22° C. and a humidity of at least 90%. Five days later, the degree of disease was rated on the following standards by the percentage of the area of lesions, and the control index was calculated.

    ______________________________________                                                        Percentage of the area                                          Degree of disease                                                                             of lesions (%)                                                  ______________________________________                                         0              0                                                                 0.5          2 or less                                                       1              3-5                                                             2               6-15                                                           3              16-30                                                           4              31-50                                                           5              51 or more                                                      ______________________________________                                          ##STR38##                                                                

The results are shown in the following Table:

                  TABLE B                                                          ______________________________________                                         Late blight of tomato (Phytophtora infestans) test                                           Concentration of the                                                                         Control                                                          active ingredient                                                                            index                                              Compound No.  ppm           (%)                                                ______________________________________                                         A-1           1000           35                                                (Comparison   500            0                                                 compound)                                                                      A-2           1000           40                                                (Comparison   500            0                                                 compound)                                                                       6            500           100                                                23            500           100                                                25            500           100                                                32            500           100                                                36            500           100                                                45            500           100                                                66            500           100                                                ______________________________________                                    

EXAMPLE C Anthracnose of cucumber (Colletotrichum lagenarium) test

Each of the test compounds in the form of an emulsifiable concentrate prepared as in Example (b) (see hereinafter) was sprayed by means of a spray gun on two-leaf stage cucumber (variety: Yotsuba) cultivated in 9 cm unglazed pots. One day after the spraying, a spore suspension of the present pathogen (Colletotrichum lagenarium) was inoculated by spraying, and the pots were left to stand overnight in a constant temperature chamber kept at 23° C. and a humidity of more than 90%. Six days later, the degree of disease was determined by the percentage of the area of lesions as in Example B, and the control index was also calculated.

The results are shown in the following Table:

                  TABLE C                                                          ______________________________________                                         Anthracnose of cucumber (Collerotrichum lagenarium) test                                     Concentration of the                                                                         Control                                                          active ingredient                                                                            index                                              Compound No.  ppm           (%)                                                ______________________________________                                         A-2           250            35                                                (comparison                                                                    compound)                                                                       1            250           100                                                23            250           100                                                31            250           100                                                32            250           100                                                36            250           100                                                40            250           100                                                65            250           100                                                68            250           100                                                69            250           100                                                73            250           100                                                75            250           100                                                78            250           100                                                79            250           100                                                81            250           100                                                ______________________________________                                    

EXAMPLE D Powdery mildew of cucumber (Sphaerotheca fuliginea) test

Each of the test compounds in the form of an emulsifiable concentrate prepared as in Example (b) (see hereinafter) was sprayed by means of a spray gun on cucumber in the two-leaf stage (variety: Tokiwa, crawling type) cultivated in 9 cm unglazed pots. One day after the spraying, a spore suspension of the present pathogen (Sphaerotheca fuliginea) was inoculated by spraying, and the pots were left to stand in a constant temperature chamber kept at 23° C. Ten days later, the degree of disease was determined by the percentage of the area of leasions as in Example B, and the control index was also calculated.

The results are shown in the following Table:

                  TABLE D                                                          ______________________________________                                         Powdery mildew of cucumber (Sphaerotheca fuliginea) test                                     Concentration of the                                                                         Control                                                          active ingredient                                                                            index                                              Compound No.  ppm           (%)                                                ______________________________________                                         A-1           100            40                                                (comparison   50             0                                                 compound)                                                                      A-2           100            0                                                 (comparison                                                                    compound)                                                                       6            50            100                                                 7            50            100                                                37            50            100                                                41            50            100                                                42            50            100                                                43            50            100                                                44            50            100                                                46            50            100                                                50            50            100                                                51            50            100                                                52            50            100                                                53            50            100                                                54            50            100                                                58            50            100                                                59            50            100                                                62            50            100                                                63            50            100                                                68            50            100                                                ______________________________________                                    

EXAMPLE E Helminthosporium oryzae test (efficacy by stalk/leave spraying)

Rice plants (variety: kusabue) were cultivated in unglazed pots having a diameter of 12 cm, and in the 3- to 4-leaf stages, a dilution of each of the test compounds prepared in accordance with Example 14 hereinafter was sprayed at a rate of 50 ml per three pots. On the next day, a suspension of artificially cultivated spores of Helminthosporium oryzae was sprayed twice onto the pots. The pots were maintained in a humid chamber having a relative humidity of 10% and a temperature of 25° C. to induce infection. Seven days after the inoculation, the degree of disease per pot was rated on a scale of 0 to 5 as follows, and the control index (%) was calculated.

    ______________________________________                                          Degree of disease                                                                            Extent of disease                                               ______________________________________                                         0              No disease                                                      1              Slight                                                          2              Small                                                           3              Medium                                                          4              Great                                                           5              Very great                                                      ______________________________________                                          ##STR39##                                                                

In this test, three pots constituted one treatment. The results are shown in the following Table:

                  TABLE E                                                          ______________________________________                                         Helminthosporium oryzae(test efficacy by stalk/leave spraying)                               Concentration of the                                                                         Control                                                          active ingredient                                                                            index                                              Compound No.  ppm           (%)                                                ______________________________________                                         A-1           250            50                                                (comparison   100            10                                                compound)                                                                      A-2           250            40                                                (comparison   100            10                                                compound)                                                                       1            100           100                                                 6            100           100                                                36            100           100                                                42            100           100                                                48            100           100                                                64            100           100                                                68            100           100                                                ______________________________________                                    

EXAMPLE F

Brown spot of rice (Helminthosporium oryzae) test/seed treatment

Seeds (variety: Koshihikari) spontaneously infected at a high rate with rice brown spot (Helminthosporium oryzae) were treated with a dilution in a predetermined concentration shown in the following table of each of the test compounds, prepared as in the method of Example (a) (see hereinafter) by each of the methods shown in the following table. On the next day, the treated seeds were sown in a seedling growing box and grown by an ordinary method. Fifteen days after the sowing, all of the seedlings were pulled out, and divided into diseased seedlings and sound seedlings. The control index was calculated in accordance with the following equation from the percentage of the sound seedlings based on the total number of seedlings based on the total number of seeds sown. The results are shown in Table F. ##EQU1##

In the table, the methods of treatment were as follows:

M-1: the seeds were immersed for 1/6 hour

M-2: the seeds were immersed for 20 hours

M-3: the seeds were covered with the powder of the compound

                                      TABLE F                                      __________________________________________________________________________     Brown spot of rice (Helminthosporium oryzae) test/seed treatment                                        Percentage of                                                                           Percentage of                                                         diseased seedlings                                                                      sound seedlings                                     Concentration                                                                              Percentage                                                                           based on the seeds                                                                      based on                                                                               Control                              Compound                                                                              of the active                                                                          Testing                                                                            germination                                                                          that germinated                                                                         the sown seeds                                                                         index                                No.    ingredient                                                                             method                                                                             (%)   (%)      (%)     (%)                                  __________________________________________________________________________     Non-treated                                                                            --     --  44.3  57.5     18.8     0                                   A-1    0.25%   M-1 62.3  38.7     38.4    24                                   (Comparison                                                                           0.025%  M-2 48.7  41.7     28.4    12                                   compound)                                                                             0.25 g/kg seeds                                                                        M-3 56.0  39.7     33.8    18                                    1     0.25%   M-1 91    0        91      89                                          0.025%  M-2 89    1.5      87.7    85                                          0.25 g/kg seeds                                                                        M-3 90    0        90      88                                   42     0.25%   M-1 92    0        92      90                                          0.025%  M-2 90    0.5      89.6    87                                          0.25 g/kg seeds                                                                        M-3 90    0        90      88                                   68     0.25%   M-1 90    0        90      88                                          0.025%  M-2 90    0        90      88                                          0.25 g/kg seeds                                                                        M-3 90    0        90      88                                   __________________________________________________________________________      Note:                                                                          The control index is the average value of three test areas each consistin      of 300 seeds.                                                            

EXAMPLE G "Bakanae disease" of rice (Gibberella fujikuroi) test/seed treatment

Seeds (variety: Koshihikari) spontaneously infected with "bakanae" disease of rice (Gibberella fujikuroi) were immersed for the period of time shown in the following table in a dilution in a predetermined concentration shown in the following table prepared in accordance with Example (a) (see hereinafter). The treated seeds were air-dried, and sown in a rice seedling growing box, and grown by an ordinary method. Up to 20 days after the sowing, the diseased seedlings were periodically pulled out and examined, and the control index (%) was calculated in accordance with the following equation. The results are shown in Table G. ##EQU2##

The control index shows an average value of three testing areas with one area consisting of 300 seeds.

                  TABLE G                                                          ______________________________________                                         "Bakanae disease" of rice (Gibberella fujikuroi) test/seed                     treatment                                                                                 Concentration Immersing Control                                     Compound   of the active time      index                                       No.        ingredient (%)                                                                               (hrs)     (%)                                         ______________________________________                                         A-1        0.5           1/6        75                                         (comparison                                                                               0.25          1/6        30                                         compound)  0.05          20         75                                                    0.025         20         28                                          1         0.5           1/6       100                                                    0.25          1/6       100                                                    0.125         1/6       100                                                    0.05          20        100                                                    0.025         20        100                                                    0.0125        20        100                                         42         0.5           1/6       100                                                    0.25          1/6       100                                                    0.125         1/6       100                                                    0.05          20        100                                                    0.025         20        100                                                    0.0125        20        100                                         68         0.5           1/6       100                                                    0.25          1/6       100                                                    0.125         1/6       100                                                    0.05          20        100                                                    0.025         20        100                                                    0.0125        20        100                                         ______________________________________                                    

EXAMPLE H

MBC-resistant "bakanae disease" of rice fungus (Gibberella fujikuroi) test/seed treatment

The "MBC-resistant bakanae disease of rice fungus" means a fungus which shows resistance to Benomyl (1-(N-n-butylcarbamoyl)-2-(methoxycarboxamido)-benzimidazole), Thiophanate-methyl (1,1'-o-phenylene-bias(3,3'-methoxycarbonyl-thiourea)) and MBC (or Carbendazim, which is benzimidazole-2-carbamide-acid-methyl-ester).

MBC-resistant "bakanae" disease fungus (the minimum growth inhibition concentration in vitro with respect to benomyl was 800 ppm) was sprayed onto rice (variety: Koshihikari) in the flowering stage. The resulting infected seeds were treated by immersion in the same way as in Example G. The results are shown in Table G. The control index was an average of three testing areas with one area consisting of 300 seeds.

                  TABLE H                                                          ______________________________________                                         MBC-resistant "bakanae disease" of rice fungus (Gibberella                     fujikuroi) test/seed treatment                                                           Concentration of the                                                                          Immersing Control                                     Compound No.                                                                             active ingredient (%)                                                                         time (hrs)                                                                               index (%)                                   ______________________________________                                         A-1       0.05           20         45                                         (Comparison                                                                    compound)                                                                      68        0.025          20        100                                         ______________________________________                                    

FORMULATION EXAMPLES Example (a) (wettable powder)

Fifteen parts of compound No. 1 of the invention, 80 parts of a 1:5 mixture of powdery diatomaceous earth and powdery clay, 2 parts of sodium alkylbenzenesulfonate, and 3 parts of a sodium alkylnaphthalenesulfonate/formaldehye condensate are pulverized and mixed to form a wettable powder. It is diluted with water and sprayed onto pathogens and/or the locus of their occurrence and the locus of occurrence of crop diseases.

Example (b) (emulsifiable concentrate)

Thirty parts of compound No. 2 of the invention, 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ester and 7 parts of calcium alkylbenzenesulfonate are mixed with stirring to form an emulsifiable concentrate. It is diluted with water and sprayed onto pathogens and/or the locus of their occurrence and the locus of occurrence of crop diseases.

Example (c) (dust)

Two parts of compound No. 3 of the invention and 98 parts of powdery clay are pulverized and mixed to form a dust. It is scattered over pathogens and/or the locus of their occurrence and the locus of occurrence of crop diseases.

Example (d) (dust)

Compound No. 4 of the invention (1.5 parts), 0.5 part of isopropyl hydrogen phosphate and 98 parts of powdery clay are pulverized and mixed to form a dust. It is scattered over pathogens and/or the locus of their occurrence and the locus of occurrence of crop diseases.

Example (e) (granules)

Water (25 parts) is added to a mixture consisting of 10 parts of compound No. 3 of the invention, 30 parts of bentonite (montmorrillonite), 58 parts of talc and 2 parts of a lignosulfonate, and they are well kneaded. The mixture is procesed by an extrusion-type granulating machine to form granules having a size of 10 to 40 mesh which are then dried at 40° to 50° C. to form granules. The granules are scattered over pathogens and/or the locus of occurrence of crop diseases. 

We claim:
 1. Compounds of the formula (VI) ##STR40## wherein R² represents fluoro-substituted lower alkyl,X represents oxygen or sulfur, Y represents halogen or lower alkyl, m represents the numbers 0, 1 or 2 and n represents the numbers 2, 3, 4, 5 or 6, Hal represents a halogen atom.
 2. 2,6-dichloro-4-(2,2,2-trifluoroethylthio)-phenol which is represented by the formula: ##STR41##
 3. 2,6-dichloro-4-trifluoromethylthio-phenol which is represented by the formula: ##STR42##
 4. 2,6-dichloro-4-trifluoromethoxy-phenol which is represented by the formula: ##STR43## 